Thermoplastic resin of a cyclic-s-triazine, an aldehyde and an aralkyl monosulfonamide



United States Patent 3 303 168 THERMOPLASTIC iiusrir OF A CYCLIC-s-TRI-AZINE, AN ALDEHYDE AND AN ARALKYL MONOSULFONAMIDE Zenon Kazenas, Euclid,Ohio, assignor to Switzer Brothers, Inc., Cleveland, Ohio, a corporationof Ohio No Drawing. Original application May 26, 1961, Ser. No. 112,785,now Patent No. 3,198,741, dated Aug. 3, 1965. Divided and thisapplication July 16, 1963,'Ser. No. 295,536

12 Claims. (Cl. 260-67.6)

The present invention relates to a new thermoplastic resin and, moreparticularly, to a thermoplastic co-condensation product in which one ofthe components is a cyclic aminotriazine, derivatives thereof or thepartial condensation products thereof with an aldehyde. The

present invention also relates to new pigment materials and, moreparticularly, to new pigments made with such thermoplasticco-condensation product. In addition, the invention relates to newcoating and casting compositions containing such pigments and the newmethods for making such compositions.

This application is a divisional of my co-pending application Serial No.112,785, filed May 26, 1961, now US. Patent 3,198,741, acontinuation-in-part of my copending application Serial No. 689,770,filed October 14, 1957, which, in turn, was a continuation-in-part of myco-pending application Serial No. 406,331, filed January 26, 1954, nowUS. Patent No. 2,809,954. Said application Serial No. 689,770 wasforfeited in favor of said copending application Serial No. 112,785.

It has now been found in accordance with the present invention that athermoplastic resin may be prepared which is a co-condensation productof a cyclic s-aminotriazine, an aldehyde and an aralkyl monosulfonamide.The new resin has a higher softening point than the wellknownsulfonamide-aldehyde resins and has some characteristics which are in noway similar to the completely condensed aminotriazine-aldehyde resinsand other characteristics which are in no way similar to thethermoplastic sulfonamide-aldehyde resins. The new resin not only has ahiger melting point than the sulfonamide-aldehyde resins, but it willrelease solvents more rapidly than such resins and does not exhibit coldflow at room temperatures as do the sulfonamide-aldehyde resins. On theother hand, the new resin, unlike the conventionalaminotriazine-aldehyde resins, is soluble in certain solvents and isthermoplastic. The over-all character of the new resin makes itespecially suitable for the manufacture of pigments. For example, thenew resin can be highly colored and, even though thermoplastic, can bereadily ground to a finely-divided condition at temperatures below about100 C. M-ost thermoplastic resins will either soften at the temperaturesencountered during grinding or will tend to ball up or agglomerate, evenat temperatures below the softening point, probably due to cold flowunder the pressure of the grinding elements. The new resin is brittleand friable below its softening point and is not horn-like and tough, asare most thermosetting resins. The new resin is insoluble in many commonvehicles and can therefore be suspended in such vehicles withoutcoalescence or agglomeration.

The new thermoplastic resin pigments of the present invention possessgreatly improved light-fastness and color brightness, which permitssubstantially thinner films to be used to obtain optimum effects,particularly with fluorescent dyestuffs, than heretofore possible withpigments available to the prior art. In addition, these pigments can beground to extremely small particle sizes without serious loss oftinctural strength, enabling them to be used "ice in many newapplications such as in printing inks, for example, letterpress inks,gravure inks, and the like. These advantages are obtained to a morenoticeable degree in daylight fluorescent pigments made in accordancewith the present invention.

Although daylight fluorescent pigments have gained wide acceptance inrecent years, the use of these pigments has been somewhat restricted bythe lack of satisfactory lig-ht-fastness and color strength and also bythe difficulties in preparing pigments of uniform fine particle size.

The original efforts at producing daylight fluorescent color effectssimply involved attempts to dissolve dyestuffs in lacquers or shellacs.However, the use of such dye solutions or spirit varnishes proved to becompletely impractical since the coatings formed had practically nolight-fastness and very little, if any, daylight fluorescence.

Later, it was found that more or less satisfactory daylight fluorescentcolor effects could be obtained with pigments in which daylightfluorescent dyestuffs were solvated in thermosetting resins ground torelatively coarse powder. However, these pigments were limited inlightfastness and color strength and could not be ground fine enough formany uses because of the tough, horn-like nature of the thermoset resin,loss of tinctural strength, bulking characteristics, and poor workingproperties when such pigments were dispersed in ink and like coatingcomposition vehicles.

Attempts were made to use thermoplastic resins which could be groundsuch as, for example, acrylonitrile polymers and copolymers, polyamides,and the like, rather than thermosetting resins in the production ofdaylight fluorescent pigments. However, when attempts were made to grindthese thermoplastic resin pigments, it was found that the pigments wereoften fibrous or elastic, or they softened at the temperaturesencountered during grin-ding, or they tended to ball up and agglomerateeven at temperatures below the softening point of the resins, or were toimpact resistant. In addition, many of these thermoplastic resins werepartially dissolved or swollen by solvents commonly employed in thepaint and ink industry. Another serious shortcoming of many of thesepigments was their inferior light-fastness particularly when daylightfluorescent dyes of the naphthalimide class were employed.

In view of the shortcomings of the thermosetting and, particularly, thethermoplastic resin pigments employed or attempted heretofore, it wastotally unexpected and completely surprising to find that the pigmentsof the present invention not only possess superior light-fastness andcolor strength, but, also, that they are brittle and friable below theirsoftening point and can be easily ground at temperatures below about C.to produce the very fine particle sizes previously desired but notattainable.

In accordance with the invention, pigments are produced by dispersing acolor material, such as a dye, in a resin which is a co-condensationproduct of an aralkyl mono-sulfonamide, a cyclic aminotriazine, and analdehyde such as formaldehyde. As disclosed herein, this may be done byany of three illustrative procedures. In accordance with two of theseprocedures, the colored resin is recovered in massive amorphous form andthen ground to the desired particle size. In accordance with the thirdof these procedures, the resin particles are first formed by grindingthe uncolored, solid, massive resin, and these particles are dyed byimmersion in an aqueous dye bath. In all three cases, the final pigmentparticles are formed by the easy grinding of a substantial nonporous,massive resin, as distinguished, for example, from merely breaking upagglomerates of fine particles pro duced by precipitation of the resinfrom a liquid solution,

or the diflicult grinding of a thermosetting resin which has been curedin the solid state.

By virtue of the brittle, friable character of the amorphous resins ofthepresent invention and the lack of porosity of the resin mass at thetime of grinding, the resins inherently break down with aconchoidal-like fracture that is characteristic of brittle, ground,amorphous materials, such as glass, and the resultant non-porousparticles, having a minimum (or complete absence) of re-entrantsurfaces, exhibit many outstanding qualities in coating compositions andparticularly in printing inks. The ground resins resist subsequentagglomeration before, during and after dispersion in a film-formingvehicle and resist settling in many such vehicles to a remarkabledegree. They have exceptionally low oil absorption characteristics andsuperior solvent release properties. They may be initially produced,stored and handled as relatively coarse sand-like particles up to thepoint of being mixed into a film-forming vehicle and are readily brokendown to the desired ultimate particle size, without balling oragglomeration, while being ground into the vehicle on a conventional3-roll mill or the like. And the, coating compositions produced withsuch pigments, particularly printing inks, have exceptional workingproperties.

In so far as the new colored pigment is concerned, it has been foundthat the light-fastness of the new pigment is better than that of othercolored pigments containing the same soluble dyestuffs available to theprior art. This characteristic renders the new resin particularlysuitable for use with yellow and red soluble fluorescent dyes such as,for example, the rhodamines (xanthenes) and the naphthalimides.

In this connection, a film of a known sulfonamidealdehyde thermoplasticresin in which brilliant yellow 66 base had been incorporated showed adecided darkening after five hours in an Atlas weather-.ometer. On theother hand, a film of completely condensed melaminealdehyde resincontaining the same dye showed an undesirable degree of darkening afterfive hours in the weather-ometer, although the darkening was not as badas in the case of the thermoplastic resin. However, a similar film ofthe new thermoplastic resin, according to the present invention, withthe same percentage of the same dye showed substantially less darkeningeffect after five hours in the weather-ometer.

The thermoplastic resin of the present invention may be prepared from anaralykyl monosulfonamide having two reactive hydrogens, i.e., tworeactive amide hydrogens, a cyclic aminotriazine or a derivative thereofhaving at least two primary amino groups, and formaldehyde orparaformaldehyde. If desired, either or both of the first-mentionedcomponents may be separately reacted with formaldehyde to form athermoplastic sulfonamidealdehyde resin or a B-stage (partiallycondensed) aminotriazinealdehyde resin, respectively, before beingcocondensed.

Advantageously, the aralkyl monosulfonamides used in the resins of thepresent invention are those in which the alkyl portion of the aralykylgroup is a short chain radical,- for example, in the range of about 1 to3 carbon atoms, with the alkyl group being attached directly to thesulfur atom of the sulfonamide group. The aryl portion is preferably abenzene nucleus, but also may be a naphthalene group. Benziylsulfonamide is one of the preferred sulfonamides for use in preparingthe thermoplastic resins of the present invention.

The cylcic aminotriazine compound may comprise a compound having atelast two amino groups as represented by the following formula:

4 wherein R is hydrogen, alkyl (preferably less than nine carbon atoms),aryl, aralkyl, amino, and the like.

The following are typical aminotriazine compounds within the aboveformula:

2,4-diamino-1,3,5-triazine 2-methyl-4,6-diamino-l 3,5 -triazine 23-hydroxy butyl) -4, 6-diamino-1,3,5-triazine2-heptyl-4,6-diarnino-1,3,5-triazine 2-phenyl-4,6-diamino-1,3,5-triazine2-benzyl-4,6-diamino-1,3,5-triazine 2,4,6-triamino-1,3,5-triazine(melamine) In place of melamine as the aminotriazine compound, one canuse methyl melamine or other alkyl derivatives of melamine (i.e.,N-alkyl melamines), such as the monoor dialkyl derivatives where thealkyl group may be methyl, ethyl, propyl, butyl, and the like, up toabout eight carbon atoms.

Also, the B-stage methylol aminotriazine (aminotriazine-aldehyde) resincan be modified by forming the alkyl ether of the methylolaminotriazine. For example, this can be done by taking an A-stagemethylol aminotriazine, i.e., the tri, tetraor pentamethylolaminotriazine, and then converting to the B-stage resin in the presenceof an alkanol such as methanol, ethanol, propanol, butanol, and similaralkanols containing up to about eight carbon atoms. When using methanol,the resin would be the monoor dimethyl ether of tri, tetraorpentamethylol aminotriazine, in partially condensed form. Also, alkanolderivatives of the aminotriazine in which the alkyl group contains morethan about three carbon atoms may be formed during the course of theco-condensation reaction by introducing the aminotriazine in a solutionof an alcohol such as butanol. It will be noted that the aminotriazinereacts as an amide rather than as an amine.

The relative quantities of the materials to be co-condensed are criticalonly to the extent that sufiicient aldehyde should be used to produce acompletely condensed product; if too large a quantity of theaminotriazine is used, the final product will be a thermosettingproduct, which is not desired; and if too small a quantity of theaminotriazine is used, the softening point of the product will differonly slightly from the softening point of the sulfonamide-formaldehyderesin and may not have insolubility in the desired solvents. Also, theamount of the sulfonamide is dependent upon the number of primary aminogroups in the aminotriazine. For example, it is preferred to use aboutthree times (on a molar basis) as much of the sulfonamide as theaminotriazine when the aminotriazine contains two amino groups, andabout five times as much sulfonamide when the aminotriazine containsthree amino groups. -In other words the aminotriazine (or B-stagealdehyde-aminotriazine resin) is preferably from about 20 to 50 molpercent of the amount of monosulfonamide (or aldehyde-monosulfonamideresin), although the former may be as great as about 70 mol percent andas little as about 17 mol percent of the latter.

Generally, when preparing the alkanol modified resin, it is necessary touse additional quantities of formaldehyde over and above that requiredfor the alkanol modification so as to provide for subsequentco-condensation with the sulfonamide-formaldehyde resin. The B-stageaminotriazine-formaldehyde resin, i.e., the methylol aminotriazine, musthave at least two methylol groups and preferably three such groups inorder to successfully carry out the subsequent co-condensation with thesulfonamide resin.

As will be noted from the following examples, the resins of the presentinvention may be prepared using as reactants either formaldehyde or itspolymer, paraformaldehyde, which polymer has the general formula (CH O)-H O, where n equals 6+. This monomer and its polymer should bedistinguished from polyaldehydes such as glyoxal containing a pluralityof aldehyde groups in a stable molecule.

The present invention will now be described in greater detail byreference to the following examples. The quantity of paraformaldehydegiven in the examples is based on 100% formaldehyde.

Example 1 360 grams of benzyl sulfonamide-formaldehyde resin were meltedat 6070 C. and then heated to 125 C. At this temperature 78.4 grams ofB-stage unmodified melamine-formaldehyde resin were added and dissolvedtherein. The solution became clear at about 135 C., and heating wascontinued up to 170 C. and held there for about ten minutes. Uponcooling, the co-condensed resin began to solidify at about 115 C. Thecompletely condensed product (94.5% yield) was a clear waterwhite resinwhich, below about 100 C. was brittle, friable, and easily ground in amicropulverizer or by wet ball milling into a finely divided powder.

Example 2 180 grams of benzyl sulfonamide-formaldehyde resin were meltedat about 60-70 C. and then heated up to about 130 C. 20 grams ofmelamine were added, and after about ten minutes the solution becameclear; then 14.3 grams of paraformaldehyde were added at 120 C. Theentire mixture was then heated up from 120 C. to between 170 C. and 175C. while stirring over a thirty minute period. The mixture was thenclear. Upon cooling, the resulting completely condensed resin began tosolidify at about 105 C. Below 100 C. the resin, which was clear andwater-white, became brittle and friable, as in Example 1.

Example 3 167 grams of benzyl sulfonamide, 29.4 grams ofparaformaldehyde, and 39.2 grams of the B-stage unmodifiedmelamine-folmaldehyde resin were heated together to a temperature ofabout 170 C. for about fifteen minutes. Upon cooling, the resultingcompletely condensed resin began to solidify at about 115 C. The resinwas clear and water-white, and below about 100 C. it was brittlev andfriable, as in Example 1.

Example 4.

168 grams of benzyl sulfonamide and 29.4 grams of paraformaldehyde wereheated together to a temperature of about 150 C., while'stirring, andmaintained at that temperature for about twenty minutes. To this resin,at 115-120 C., were added 39 grams of the B- stage unmodifiedmelamine-formaldehyde resin, and the mixture was heated up to 170 C. forfifteen minutes. The'resulting completely condensed resin had asoftening point of 115 C. and physical characteristics substantially thesame as in Example 1, 2, and 3.

Example 5 To 155 grams of formalin (38% concentration) was addedsuflicient KOH (20% solution) to adjust the pH value of the formalin toabout 9. Then 168 grams of benzyl sulfonamide were added. The mixturewas heated to 100 C. and maintained at that temperature until all waterhad been evaporated. The temperature was then raised to 150 C. and heldthere for 10-15 minutes. About 180 grams of the sulforiamide-aldehyderesin was formed. To this resin, at 115 C., was added 39 grams of theB-stage melamine-aldehyde resin, and the mixture was then heated up to170 C. with stirring and held at that temperature for 15-20 minutes. Theresulting completely condensed product, as in the prior examples,softened at about 115 C. and was brittle and friable below about C.

Example 7 196.7 grams of benzyl sul'fonamide were heated to C. 36.4grams of paraformaldehyde (95%) were then added slowly with mechanicalstirring until thoroughly mixed. 71.7 grams of2-phenyl-4,6-diamino-1,3,5- triazine and 31.85 grams of additionalparaformaldehyde were added with stirring. When the materials werethoroughly mixed, the temperature was raised to 175- 180 C. over aperiod of about 40 minutes and held at that temperature for anadditional 10 minutes, during which time excess formaldehyde in thereaction mixture was distilled off. The resulting completely condensedproduct (87.4% yield) had the physical characteristics of the resins inthe foregoing examples.

Example 8 The procedure of this example was the same as Example 7 exceptthat 84.3 grams of 2-benzyl-4,6-diamino- 1,3,5-triazine were substitutedfor the 2-phenyl-4,6-diamino-1,3,5-triazine. The physicalcharacteristics of the resulting completely condensed product weresubstantially the same as the resins of the foregoing examples.

Example 9 The procedure of this example was the same as Example 7 exceptthat 62.9 grams of 2(beta-cyanoethyl)-4,6 diamino-1,3,5-triazine weresubstituted for theZ-phenyl- 4,6-diamino-1,3,5-triazine. The resultingcompletely condensed product had the physical characteristics'of theresins of the foregoing examples.

Example 10 v The procedure of this example was'the same as Example -7except that 78.9 grams of diallyl melamine were substituted for the2-phenyl-4,6-diamino-l,3,5-triazine. The resulting completely condensedproduct had the physical characteristics of the resins of the foregoingexamples.

Any of the foregoing clear resins can be colored to form the pigments ofthe invention by introduction of the coloring material at a suitablestage up to and including production of the resin in finely-dividedform. In preparing fluorescent pigments from xanthene, naphthalimide,land/or coumarin fluorescent dyes, it is highly desirable that the dyeor dyes be completely dissolved in the resin. Additionally, the resinmay be colored by other coloring materials, including otherresin-soluble dyes, organic or inorganic pigments, flatting andopacifying agents, or the like, by dispersing any such coloringmaterials in the resin.

Examples 11 through 17 illustrate formulations for a number of differentdyes which may be combined with the clear resins of Examples 1 to 10 byadding the dye when the mixture has reached :a temperature of between C.and C., while heating up to C., or by remelting the finished resin andadding the dye to the melt. The amount of dye given in each example isthe amount used for each 100 grams of clear resin.

Example 11 When 1.97 grams of brilliant yellow 66 base (4-amino1,8-naphthal-2,4-dimethyl phenylimide) and 0.22 gram of rhodamine 6 GDNExtra (Color Index No. 752) are incorporated in the resin, the finalproduct has an orangeyellow color which is strongly daylight fluorescentwhen 7 applied to surfaces by various printing methods. The dyesemployed in this case are a combination of a fluorescent naphthalirnidedye and a fluorescent xanthene dye.

Example 12 If 0.97 gram of rhodamine B Extra (Color Index No. 749) and0.97 gram of rhodamine 6 GDN Extra are incorporated in the resin, theresulting colored resin pigment is a bluish-red which is also stronglydaylight fluorescent when applied to a surface as an ink. The dyesemployed in this case are a combination of two xanthene dyes.

Example 13 r If 3.0 grams of brilliant yellow 6G base (fluorescentnaphthalimide dye) are incorporated in the resin, the resulting pigmentis a lemon yellow which is also highly daylight fluorescent.

1 Example 14 If 0.33 gram of rhodamine B Extra and 0.5 gram of rhodamine6 GDN Extra (two fluorescent xanthene dyes) and 1.0 gram of brilliantyellow 6G base are incorporated in the resin, the resulting pigment is afiery-orange and is highly daylight fluorescent.

In addition to the particular fluorescent xanthene dyes used in theforegoing examples, one may use other fluorescent xanthene dyes such as,for'example, Xylene red (Col-or Index No. 748), rhodamine G (Color IndexNo. 746), rhodamine G (Color Index No. 750), or rhodamine 2B (ColorIndex No. 751).

In addition to the particular fluorescent naphthalimide dye used in theforegoing example-s, one may use other fluorescent naphthalirnide dyes,such as, for example:

4 N-butyl-amino) 1,8 naphthal n-butyl imide 4 amino 1,8 naphthal p-xenylimide Depending upon the particular pigment color desired, one mayemploy any of the fluorescent napthalimide and fluorescent xanthenedyes, individually, or in combination with each other, or in combinationwith other coloring materials of the character recited above.

The proportion of the fluorescent dye is not critical, but is dependentupon the particular color desired and the particular dye or combinationof dyes employed. Amounts as high as 4% or more have been usedsuccessfully.

While the superior light-fastness of pigments made by incorporatingcoloring material in the resins herein disclosed is particularlypronounced when the coloring material comprises one or more of thefluorescent naphthalimide and fluorescent xanthene dyes, the inventionis not so limited, and other fluorescent or non-fluorescent dyes ormixtures thereof may be used to advantage as shown in the followingExamples 15, 16, and 17.

Example 15 If 0.97 gram of malachite green (Color Index No. 657) areincorporated in the resin, the product has the characteristic greencolor of that dye.

Example 16 The incorporation of 1.0 gram of 4-methyl-7-diethylaminocoumarin in the resin produced a colorless resin which could be easilyground to a fine powder and which give a bright blue color when exposedto ultraviolet light.

Example 17 360 grams of benzyl sulfonamide resin were melted at 6070 C.and then heated to 115 C., at which point a mixture of 37.35 grams ofcadmium primrose (a nonfluorescent yellow cadmium sulfide pigment soldby Harshaw Chemical Co.) dispersed at 37.35 grams of water was addedwith stirring and the heating continued. When the temperature reached125 C., 78.4 grams of B-stage unmodified melamine-formaldehyde resinwere added and dissolved therein. The mixture was then heated until thetemperature reached 150" C., at which point 4.15 grams of rhodamine BExtra were added. Heating was continued until the temperature reachedabout 170 C., and then was held at this temperature for about 10minutes. The resulting pigment was abn'ght red and was highly daylightfluorescent.

Other non-fluorescent coloring materials also may be employed incombination with the fluorescent coloring materials in the same mannerthat the mixture of rhodamine B Extra and cadmium primrose was employedin Example 17. For example, 5% of rutile titanium dioxide, 10% oflithopone or 9% of chrome yellow may be dispersed in one of thefluorescent thermoplastic resin pigments of the present invention toproduce different color effects.

If desired, a colorless ultraviolet absorbing agent such as a nearlypure substituted benzophenone may be added in combination with thefluorescent dyes of Examples 1114 and 17. The incorporation of 1% of asuitable nearly pure substituted benzophenone enhances the stability ofthese pigments to daylight. The addition of ultraviolet absorbing agentsto daylight fluorescent pigments is the subject of Switzer et al. PatentNo. 2,653,109.

In Examples 11 to 17, pigments were prepare-d by the preferred method ofintroducing the dyestutf in the molten resin. If desired, the undyedresin may be prepared in its final, solidified, finely ground state byany of the conventional grinding procedures, following which the finelyground resin may be immersed in a dye bath to incorporate one or moredyes and produce a colored pigment. Alternatively, the solidified resinand the dye or dyes may be dissolved in a ketone or an ester solvent,the solvent evaporated, and the resulting colored resin then ground topigment form. These optional procedures are illustrated in the followingExamples 18 and 19:

Example 18 A dye bath was prepared as follows:

Water cc 40 Iso-octyl phenyl, ether of polyethylene glycol, known asTriton X-l00 gram.. 1.0 Formic acid solution) cc 10.0 Rhodamine B Extragram .05 Rhodamine 6 GDN Extra do .05

The above materials were dissolved to form a 0.2% dye bath, and 5 gramsof the powdered resin of Example 1 were added. The dye concentration was2% based on the weight of the resin. The dye bath and resin were warmedto hasten incorporation of the dye in the resin, to a temperature notabove. 46 C. for three minutes, and the dyed resin was then filteredfrom the bath and washed with cold water until the water wassubstantially colorless. By comparing the color of the dyed resin andthe color of a resin containing 1% of the same dyes which had beenincorporated during manufacture as in Example 12, it was estimated thatthe resin powder contained 1% of the dyes.

Example 19 grams of the resin of Example 1, before being ground, weredissolved in 300 grams of acetone along with 0.5 gram of rhodamine BExtra and 0.5 gram of rhodamine 6 GDN Extra. After mixing thoroughly,the acetone was evaporated to leave the dyed resin in solid massiveform, and the thus dyed resin was ground to pigment fineness to plroducea pigment comparable to that produced in Examp e 18.

The pigments prepared in the manner described in the foregoing examplesare insoluble inwater and aliphatic hydrocarbon solvents, arepractically insoluble in arcmatic hydrocarbon solvents, and are solubein ketones and solvent esters.

Based on the physical characteristics mentioned herein, the pigments ofthe present invention may be used in a Wide variety of liquid vehiclebinders to form protective and decorative paints, enamels, or lacquers,silk screen inks, letterpress inks, self-sustaining resinous films,molded or extruded articles, and the like. In general, the suitablevehicle binders for obtaining the maximum benefits from the inventionare those which are capable of being transformed to solid form byoxidation, solvent evaporation, or polymerization or a combination ofsuch processes, and in which the pigments of the invention aresubstantially insoluble so that the pigments may be dispersed in thevehicle as undissolved, finely-divided particles. However, the pigmentsof the invention may also be used in vehicles in which they aredissolved so that the pigment becomes, in effect, a part of the vehicleitself. Obviously, where fluorescent pigments are employed, the vehicleshould be substantially transparent, though not necessarily colorless,in order to obtain the full benefit of the fluorescent properties of thepigments.

The many types of vehicle binders which may be advantageously coloredwith the pigments of the present invention to produce novel pigmentedcompositions are illustrated by the following additional examples. Inall of these examples, the parts and percentages given are by Weight.

The two following examples illustrate, respectively, an alkyld base silkscreen ink and a lacquer type silk screen ink, both containing the newpigment suspended in a vehicle:

Example 20 Parts Long oil alkyd (soya type50% solids) 40.6 Aluminumstearate gel 8.6 Driers (metal naphthenates) 0.3 Mineral spirits 6.5

Pigment as per Example 11 using resin of Example 1 44.0

The above ink, when applied by the silk screen process, driesprincipally by oxidation to a hard film and produces a bright yellowcolor having a slightly orange tint.

In the foregoing example, the alkyd resin may be replaced in the sameformulation with a linseed oil varnish, or a phthalic .anhydride-castor-oil alkyd varnish of 60% solids, or a phthalic anhydride-linseed oilalkyd varnish of 60% solids.

Example 21 Vehicle: Parts Styrene-butadiene resin 40 Aromatic petroleumsolvent having a KB value of 70 to 90 60 To 30 parts of the abovevehicle, add 4 parts of methyl dihydroabietate and 28 parts of any ofthe pigments of Examples to 18 to produce the desired color. If desired,the resin in the above vehicle may be replaced by a mixture containingabout 30 parts of cyclized rubber and 10 parts of a low molecular weightpolystyrene, in which case the methyl dihydroabietate may be omitted.

The compositions of Example 21 will dry essentially by solventevaporation to .a hard colored film, and drying may be accelerated bythe application of heat, if desired. Although formulated primarily as asilk screen ink, the composition may suitably be used as a coatingcomposition for brush or spray application by adjustment of the amountof petroleum solvent to produce the desired consistency.

10 The following example illustrates a letterpress printing inkcontaining the new pigment suspended in a vehicle:

Example 22 Parts No. 3 heat bodied linseed oil 10 Pigment as per Example15 using resin of Example 1 l5 Kerosene 6 Lead and manganese linoleates3 Calcium sulfonate of mahogany acids Q. 1

This material is dispersed on a conventional three-roll ink mill. Theprinting ink of this example will air dry, but, if desired, drying maybe accelerated with heat in accordance with common practice in the useof printing inks.

The following example illustrates a paint containing a new pigment ofthe invention in combination with a conventional pigment:

Example 23 Parts Long 011 alkyd (castor oil type-54% solids) 50 Driers(metal naphthenates) 0.7 Mineral spirits 10 Cadmium primrose 4.5 Pigmentas per Example 12 using resin of Example 1 50 Example 24 The ingredientsof the following components A and B are separately mixed, as by ballmilling:

Component A:

Chloro sulfonated polyethylene containing about 27% chlorine and 1.5%sulfur and polymerized to solid form Parts Xylol 160 ComponentB:

Light calcined magnesium oxide 7.4 Pigment as per Example 13 using resinof Example 1 30.0 Xylol 85.6 Mercaptobenzothiazole .8 Diphenyl guanidine.2 Hydrogenated resin 1.0

40 parts of Component A and 24.4 parts of Component B are thenthoroughly mixed to produce a sprayable coating composition that sets inpart by solvent evaporation and in part by vulcanization or condensationand has a pot life of about 4 hours at room temperature. Minor dilutionsto adjust the viscosity for spraying may be made with xylol or toluene.The cure may be effected at room temperature or may be accelerated byheating at temperatures up to about C. for 20 to 30 minutes.

The following example is illustrative of a plastisol suitable forcasting or molding into finished solid objects:

Example 25 Parts 95% vinyl chloride-% vinyl acetate copolymer 50 Dioctylphthalate 12.5 Dioctyl sebacate a 12.5 Pigment as per Example 14 usingresin of Example l 2O Epoxy resin stabilizerl75 to 210 epoxideequivalents (Shell Epon 828) 3 When this plastisol is cast or moldedinto bodies of appreciable thickness, it is heat cured at about 350 3 60F. for long enough to reach this temperature throughout the mass whichmay require from to 20 minutes. When formed into thin films or thinwalled bodies, curing for from 3 to 5 minutes at that temperature willsuffice.

The composition of this last example may be diluted by adding up toabout parts of V.M. & P. naphtha or 15 parts of a 50% mixture of V.M. &P. naphtha and toluol to 85 parts of the plastisol to produce anorganosol which may be more easily spread into thin films for makingselfsustaining, colored, transparent sheet materials or thin walledbodies.

Examples to have been given primarily to show that the pigments of thepresent invention, when colored with a fluorescent naphthalimide or afluorescent xanthene dye, are not limited in their utility to beingsuspended in a particular type of vehicle binder, either as regards thechemical character of the vehicle or the physical properties whichrender the vehicle suitable for difierent uses. The light-fastness,color strength, and fluorescent properties of the resultant productscompared to the same vehicle compositions containing prior art pigmentsare imparted primarily by the new pigment resin employed in accordancewith the invention as a solvent for the dye. Such improved propertiesare achieved to the most pronounced degree when the vehicle binder hasthe new pigment or pigments dispersed therein in an undissolved,finely-divided state, as illustrated by Examples 20 to 25. As should beevident from the variety of different vehicle binders disclosed, thisimprovement is independent of the chemical composition of the vehiclebinder and of the process by which it is converted to a solid state, solong as the vehicle binder is not a solvent for the pigment and issubstantially transparent so as to permit the fluorescent properties ofpigment particles within the body of the solidified binding medium to beeifective.

The following example illustrates a coating composition in which thepigment of the invention is dissolved in I the vehicle binder:

Example 26 For coating wood, the following formulation may be used:

Parts Pigment as per Example 12 using resin of Example 1 14 Lowviscosity cellulose butyrate 22 Dioctyl phthalate plasticizer 12 Methylethyl ketone 25 Ethyl acetate 25 Toluene 10 Although the presentinvention has been described with reference to the foregoing examples,it will be understood that various modifications will occur to thoseskilled in the art, and it is intended that such modifications as comewithin the scope of the appended claims he covered thereby.

What is claimed is:

1. A completely condensed, thermoplastic resin consisting essentially ofthe condensation product of at least one aldehyde entirely selected fromthe class consisting of formaldehyde and paraformaldehyde, at least onearalkyl monosul fonamide having two reactive amide hydrogens, the .alkylportion of the aralkyl group of said monosulfonamide containing about 1to 3 carbon atoms and being attached directly to the sulfur atom of thesulfonamide group, and at least one aminotriazine having at least twoamino groups, the amount of said aminotriazine being suificient torender said resin substantially insoluble in aromatic hydrocarbonsolvents but insufficient to render it thermosett-ing.

2. A completely condensed, thermoplastic resin according to claim 1 inwhich the amount of said aminotriazine does not exceed '70 mol percentof said monosulfonamide.

3. A completely condensed thermoplastic resin according to claim 1 inwhich said aralkyl monosulfonamide is benzyl sulfonamide.

4. A completely condensed, thermoplastic resin according to claim 1 inWhich said aminotriazine is melamine.

5. A completely condensed, thermoplastic resin according to claim 1 inWhich said aminotriazine is 2-phenyl-4,6-diamino-l,3,5-triazine.

6. A completely condensed, thermoplastic resin ac cording to claim 1 inwhich said aralkyl monosulfonamide is benzyl sulfonamide and saidaminotriazine is melamine, the amount of said melamine being betweenabout 17 and 50 mol percent of said monosul'fonamide.

7. A process of :producing a thermoplastic, resinous condensationproduct comprising completely co-condensing, at a temperature notexceeding C., a fluid reaction mass consisting essentially of a firstcomponent (A) selected from the class consisting of (a) a mixture of atleast one aldehyde entirely selected from the class consisting offormaldehyde and paraformaldehyde and at least one aralkylmonosulfonamide having two reactive amide hydrogens, the alkyl portionof the aralkyl group of said monosulfonamide containing about 1 to 3carbon atoms and being attached directly to the sulfur atom of thesultfonamido group, and b) a thermoplastic condensation product of theconstituents of mixture (a), and a second component (B) selected fromthe class consisting of (c) a mixture of at least one aldehyde entirelyselected from the class consisting of formaldehyde and paraformaldehydeand at least one aminotriazine having at least two amino groups, and (d)a thermofusible partial condensation product of the constituents ofmixture (0), the amount of said second component (B) being sufiicient torender said completely condensed, thermoplastic, resinous condensationproduct substantially insoluble in aromatic hydrocarbon solvents butinsufiicient to render it thermosetting.

8. A process of producing a completely condensed,

thermoplastic, resinous condensation product according.

to claim 7 in Which the amount of said aminotriazine does not exceed 70mol percent of said monosulfonarmide.

9. A process of producing a completely condensed, thermoplastic,resinous condensation product according to claim 7 in which said aralkylmonosulfonamide is benzyl sulfonamide.

10. A process of producing a completely condensed, thermoplastic,resinous condensation product according to claim 7 in which saidaminotriazine is melamine,

11. A process of producing a completely condensed,

13 14 thermoplastic, resinous condensation product according ReferencesCited by the Examiner to claim 7 in which said .aminotriazine iS2-phenyl-4,6-

diamino-1,3,5-tri-azine.

12. A process of producing a completely condensed, 2,366,494 1/1945DAlelio 260-556 thermoplastic, resinous condensation product according 52,809,954 10/1957 Kazenas 26067-6 to claim 7 in which said aralkylmonosulfonarnide is 2,938,873 5/1960 Kazenas 252 301'2 benzylsulfonamide and said aminotriazine is melamine, the amount of saidmelamine being between about 17 WILLIAM SHORT P r y Exammer and 50 molpercent of said monosul-fonamide. J. C. MARTIN, Assistant Examiner.

1. A COMPLETELY CONDENSED, THERMOPLASTIC RESIN CONSISTING ESSENTIALLY OF THE CONDENSATION PRODUCT OF AT LEAST ONE ALDEHYDE ENTIRELY SELECTED FROM THE CLASS CONSISTING OF FORMALDEHYDE AND PARAFORMALDEHYDE, AT LEAST ONE ARALKYL MONOSULFONAMIDE HAVING TWO REACTIVE AMIDE HYDROGENS, THE ALKYL PORTION OF THE ARALKYL GROUP OF SAID MONOSULFONAMIDE CONTAINING ABOUT 1 TO 3 CARBON ATOMS AND BEING ATTACHED DIRECTLY TO THE SULFUR ATOM OF THE SULFONAMIDE GROUP, AND AT LEST ONE AMINOTRIAZINE HAVING AT LEAST TWO AMINO GROUPS, THE AMOUNT OF SAID AMINOTRIAZINE BEING SUFFICIENT TO RENDER SAID RESIN SUBSTANTIALLY INSOLUBLE IN AROMATIC HYDROCARBON SOLVENTS BUT INSUFFICIENT TO RENDER IT THERMOSETTING. 